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Molecules 2016, 21(8), 999;

Intramolecular Chain Hydrosilylation of Alkynylphenylsilanes Using a Silyl Cation as a Chain Carrier

Faculty of Education, University of Miyazaki, 1-1 Gakuen Kibanadai Nishi, Miyazaki, 889-2192 Miyazaki, Japan
Department of Chemistry, Gakushuin University, 1-5-1 Mejiro, Toshima-ku, 171-8588 Tokyo, Japan
Graduate School of Science and Technology, Gunma University, 1-5-1 Tenjin-cho, Kiryu, 376-8515 Gunma, Japan
Authors to whom correspondence should be addressed.
Academic Editor: Mitsuo Kira
Received: 9 July 2016 / Revised: 25 July 2016 / Accepted: 27 July 2016 / Published: 1 August 2016
(This article belongs to the Special Issue Advances in Silicon Chemistry)
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Diorganyl[2-(trimethylsilylethynyl)phenyl]silanes 1ac and methyl-substituted phenylsilanes 1d and 1e were treated with a small amount of trityl tetrakis(pentafluorophenyl)borate (TPFPB) as an initiator in benzene to afford the corresponding benzosiloles (2ae) in moderate to good yields. However, no reaction was observed for the reaction using [2-(1-hexynyl)phenyl]diisopropylsilane lf. The methyl substituent was tolerated under the reaction conditions and increased the yield of the corresponding benzosilole depending on the substitution position. From the result using 1f, the current reaction was found to require the trimethylsilyl group, which can stabilize intermediary alkenyl carbocations by the β-silyl effect. The current reaction can be considered an intramolecular chain hydrosilylation of alkynylarylsilanes involving silyl cations as chain carriers. Therefore, the silyl cations generated by hydride abstraction from hydrosilanes 1 with the trityl cation causes intramolecular electrophilic addition to the C-C triple bond to form ethenyl cations, which abstract a hydride from 1 to afford benzosiloles 2 with the regeneration of the silyl cations. View Full-Text
Keywords: benzosilole; silyl cation; hydrosilylation; metal free benzosilole; silyl cation; hydrosilylation; metal free

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Arii, H.; Nakabayashi, K.; Mochida, K.; Kawashima, T. Intramolecular Chain Hydrosilylation of Alkynylphenylsilanes Using a Silyl Cation as a Chain Carrier. Molecules 2016, 21, 999.

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